Pyridinium derivatives of phenoxyalkanol esters



Patented Aug. 1, 1950 PYRIDINIUM DERIVATIVES OF PHENOXYALKANOL ESTERS Melvin De Groote, University City, and Bernhard Keiser, Webster Groves, Mo.,

assignors to Petrolite Corporation, Ltd., Wilmington, DeL, a corporation of Delaware No Drawing. Original application April2, 1945,

Serial No. tion This invention relates to a new chemicalprodnot or compound and to the manufacture of same, our present application being a divisionof our pending application Serial No. 586,262, filed April 2, 194-5, now Patent No. 2,429,996.

One object of our invention is to provide a new material or composition of matter, that is particularly adapted for use as a demulsifier in the resolution of crude oil emulsions, but which is also capable of use for various other purposes, or in various other arts.

Another object of our invention is to provide a practicable method for ducing the new material ter above referred to. H

The new material or composition of matter herein described consists of a hydrophile pyridine compound of the formula:

Halogen in which. R is the radical obtained by the ryen moval of an alpha-hydrogen atom from the acid radical of a low molecular weight mono-carboxy acid ester of a phenoxyalkanol of the formula:

in which R1 is a monocyclic phenylradical having at least 2 and not more than 3 alkyl side chains, at least 2 of which contain at least 4 carbon atoms and the longest of which does not contain more than 3 carbon atoms, with the proviso that the number of carbon atoms in all the side chainsmust total at least 9; RzOqiS an alkoxy radical selected from the class consisting of C2H4O and --C3HcO'- radicals; and n is a small whole number varying from 1 to 3, or even 4 or 5, or more-for instance, 6. More specifically, the ester derived from a phenoxyalkanol includes alkanols in which the carbon atom chain is interrupted at least once by oxygen; i. e., etheralkanols or etheralcohols, Thus, R, in the first formula of the text, represents the monovalent radical by elimination of halogen from the ester of the formula:

R1O(B2O)1LOCLR3 Halogen manufacturing or proin which all the symbols have their or composition of matprior signifi canceyand OCRs Halogen is the acyl radicalof 586,262. Divided and this applica- November 26, 1945, Serial No. 630,977

9 Claims. (01. 260-295) a low molecular weight acid, such as chloroacetic acid. In other words,

repeating the previous example with specific reference to chloroacetic acid, the formula becomes:

R1O(R2O) nOC.CI-I2Cl Briefly stated, the preparation of our new material or composition of matter contemplates three steps: In the first step a properly selected phenol of the kind typified by the formula RlOH istreated with 1 to 3 moles or even 4 or 5 moles of an oxyalkylating agent of the kind described, or,at least sufiicient to insure at least incipient hydrophile properties in the final compound, so asto produce a phenoxyalkanol; employing ethylene oxideas an example, the reaction may be illustrated in the following manner:

The second step consistsin esterifying the alcohol thus obtained with a suitable alpha-chloromonocarboxy acidQsuch as chloroacetic acid, so as to form the corresponding ester. This reaction may beillustrated in the following manner:

R1oo2Hloji; -;f i o'joo.omo1 The third or final step consists in reacting the ester so obtained with pyridine, or one of its homologs, as subsequently specified. Such reac-\ tion may be shown in the following manner:

aloozmoooomoi+ alocinloooonzi vi alpha-choromonocarboxy suitable are, for example, a-chloropropionic'acidy etc., but especially any acid of the formula:

B R-(3-COOH where R is a hydrogen atom or'a methyl radical.

Substituted phenols of for reaction, in preparation of the herein described compounds, include, among other, di(tertiary) amylphenol, diheptylphenol dioctylphenol- 2,3-dimethy1-'i=G-diJ-ter F (di-diisobutylphenol) butylphenol; 2-ethyll,6-di tert --butylphenol; 2-methyl-a,6-di-tert-butylphenolg 8-ethy-1-4,6 ditert-butylphenol; 4 ethyl 2,6 di tert butylphenol; e methyl 2,6- diiert amy1phenol; and 2, 1,6=tri-tertdmtylphenol.

Treatment of water-insoluble phenols with alkyleneoxides ofthekind enumeratedi. e., with ethylene oxide and propylene oxide, is a wellknown procedure. Such compounds are frequentlyoxyethylated soas to render them watersoluble. In the present instance instead of treatingonemole of the selected phenol with a large ration'of oxyalkylating agent, one employsinstead a comparatively low ratio, as indicated by the value for the letter win prior formulae. In other words, one treats .the phenol with 1'mole,.2 moles, or 3 moles, or even more moles of the oxyalkylating agent. The product .so obtained is still dis ti nctly water-insoluble to theextent that" it will not yield a sol or solution, and this is also true of the ester derived therefrom. The ester is in-' variably even less water-soluble. It is-to be noted,

however, that such water-insoluble, or partially soluble, product represents the initial .oxyalkyla tiorvstep in the same type of procedure employed to produce a water-soluble product, or, atleast, a product of distinctly hydrophile properties. Thus, as an example of variouspatents which teach the oxyalkylation of water-'insoluble phenols including the stepwise addition .of the .oxyalkylating agent, attention is directedto the-follQWi-ng: British'Patent No. 470.181, British Patent Ito-452,866, U. S. Patent No. 2,2. l3,330, dated May 2'7, 194-1,-to De Groote and Kaiser, and U. S. Patent No. 2,233.381, dated February 25, 1 941, toDe Groote and Keiser.

Having obtained a water-insoluble phenoxyalkanol, or one that is somewhat hydrophile, such product is esterified with chloroacetyl chloride, ohloroacetic acid, bromoacetic'acid, alpha-chloropropionic acid, or the'like. Such reaction, particularly between the acid itself, as differentiated from the acylchloride, is simply an esterification reaction, with the elimination of Water, and is preferably carried out in the presence of an-inert solvent insoluble in vvater,vvhich'serves to remove the water of formation. Such procedure i illustrated by numerous patents, including the following: British Patent No. 500,765; U. S. Patent No. 1,732,392, dated October 22, 1929, to Wietzel, and U. S. Patent No. 2,264,759, dated December 2, 1941, to Jones.

Having obtained the ester, it is reacted with the kind contemplated pyridine or a pyridine homolog. This reaction takes place readily by merely refluxing, in the presence of an excess of pyridine, and subsequently removing the excess of pyridine which does not enter the reaction by distillation and preferably vacuum distillation. The herein de scribed procedures are illustrated by the following examples:

PHENOXYALKANOL Example 1 One pound mole of tri-isobutylphenol C die-L- is'tre'atedwith lel pounds of ethylene oxide in the presence of approximatelythree-fourths of a pound of suspended sodium methylate. As the reaction proceeds-thesodium methylate either dissolves or is converted into a soluble compound by chemical combination. Reaction is conducted at approximately 125 C. and -250 pounds gauge pressure forapproximat-ely anhour and a halfcto two and one-half 'hoursuntil the reaction appears to be complete, as evidenced by the pressure droppingtozero.

PHE XYAL QL Example 2 1 an additional portion of ethylene oxide (approximately &4; pounds) and this reaction is conducted at approximately C. with a gauge pressure of approximately 100 pounds, until all of the ethylene oxide-is absorbed] Time required for reaction is approximately the same as required in previous example.

PHENOXYA'LKANOL Example 3 I The same procedur .is repeated as in. the prior example, except that 2 pound moles of ethylene oxide, to wit, 88 pcunds,,are employed and the period of time required to complete the reaction may vary from approximately 1 hour to about 3 hours. Further oxyethylation, for instance, the use of another 88 pounds of ethylene oxide, may be required to give a distinct hydrophile effect in thefinal compound.

PHENOXYALK ANOL Example 4 Onepound mole of 2,4-di(tertiary)amylphenol is-reacted in the same manner as in the 3 prior examples, with ethylene oxide, so as toproduce compounds having 'the following composition:

in which 11, varies from 1 to 3.

'PI-IENOXYALKANOL Example 5 The same procedure is followed as in the preceding-five-examples, except that propylene oxide is substituted for ethylene oxide. As suggested by the patents previously referred to in regard to oxyethylation, such less active oxyalkylating agent requires a somewhat higher temperature, for instance, a maximum of 200 C. and a somewhat higher pressure, for instance, a maximum of 300 pounds, and a somewhat longer period of reaction, for instance, approximately twice the period of time required for ethylene oxide.

Previous reference has been made to the fact that the esterification step is carried out in the conventional manner, preferably in the presence of an inert solvent. This simply means that thereactants, to wit, the acid, such as chloroacetic acid, and the phenoxyalkanol, are mixed in-equimolar proportions, in the presence of a solvent in which both are soluble, such as xylene,

cymene, decalin, or the like. The mixture is refluxed at some suitable temperature, above 100 C. and below 200 C., so that water of formation resulting from the esterification reaction is carried over as a constant boiling mixture. Such mixed vapor is condensed in the customary manner, so the water is trapped off, measured and then discarded and the solvent returned to the reaction vessel for further use. Ordinarily, such reactions are catalyzed by the addition of an acidic catalyst, such as toluene sulfonic acid, a cresyl phosphoric acid, dry hydrochloric acid, trichloroacetic acid, or the like. Insofar that the alpha-chlorocarboxy acids show marked acidity, I

in" comparison with the unchlorinated carboxy acids, the reaction may be conducted without an added catalyst, if desired, or in the presence of an added catalyst, such as one-half percent to 1% of toluene sulfonic acid. Such catalyst tends to discolor the final product, but this isoften immaterial, as, for example, when the. product is used as a demulsifier. The entire procedure is too well known to require further elaboration, but is illustrated by the following examples:

ESTER Example 1 liquid.

ESTER Example 2 The same procedure is followed as in the preceding example, except that phenoxyalkanols, exemplified by Phenoxyalkanol, Examples 2 to 5', inclusive, are substituted for the phenoxyal kanol employed in the preceding example.

ESTER.

Example 3 The same procedure is employed as in the two preceding examples, except that a-chloropropionic acid is substituted for alpha-chloroacetic acid.

ESTER Example 4 Chloroacetylchloride is substituted for the chloroacetic acide in Ester, Example 1. The reaction starts to take place rapidly between 45 C and C. and the temperature should be controlled so the reaction takes place at the lowest suitable temperature. The acyl chloride should be added slowly to the phenoxyalkanol, with constant and vigorous agitation. Hydrochloric acid is formed and should be vented and disposed of in a suitable manner. If the reaction does not take place promptly, the temperature should be raised moderately, for instance, 5 to 15 C., or a bit higher, until the reaction proceeds smoothly. However, as soon as the reaction does start, the temperature should be lowered until the reaction proceeds at the slowest feasible rate. Generally, this means use of proper cooling devices, or controlled slow addition of the acyl chloride. Completeness of the reaction can be determined in any suitable manner, such as a check on the amount of hydrochloric acid eliminated, or the drop in hydroxyl value of the reactant mixture. When the reaction is complete, any hydrochloric acid gas dissolved in the reaction mass should be eliminated by passing an inert gas, such as carbon dioxide, through the mixture.

Having obtained an ester of the kind exemplified by the previous examples, or the bromo derivative instead of the chloro derivative, the next step simply involvesreaction with pyridine or a pyridine homolog of the kind previously described. The reaction takes place fairly rapidly, and usually is complete within four to 20 hours, particularly if an excess of pyridine is, employed. The esters previously described are invariably viscous or semi-solid masses, which are soluble in pyridine without difiiculty.

QUATERNARY PYRIDINIUM HALIDE Example 1 One pound mole of the ester described in Ester, Example 1, preceding, is refluxed with constant stirring, with several pound moles of technically pure pyridine. The reaction is conducted from approximately 4 to 20 hours, at a temperature in excess of C., or thereabouts, until reaction is complete. Completeness of the reaction can be determined by distilling the uncombined pyridine from a sample and noting, by difierence, percentage of pyridine which has been combined. Another suitable test is the determination of ionizable halogen, for instance, chlorine. It is to be noted that the reaction converts a nonionizable halogen atom to an ionizable atom. When the reaction is complete, the excess of pyridine is removed by continuing the stirring and employing vacuum, so as to give a substantially solid or highly viscous, dark-colored mass. This reaction product should show distinct hydrophile properties.

QUATERNARY PYRIDINIUM I-IALTDE Example 2 The same procedure is followed as in Example 1, preceding, except an ester exemplified by Ester, Example 2 and Ester, Example 3, preceding, is substituted for the ester employed in the previous example.

QUATERNARY PYRIDINIUM HALIDE Example 3 The same procedure is followed as in immediately preceding Examples 1 and 2, but instead of using technically pure pyridine, one employs a commercial pyridine, in which there is present some monomethylpyridine and dimethylpyridine, in addition to unsubstituted pyridine.

ass-woes lfh vnew "ma erials or compos ions of ma ter herein described, are-useful as wetting, detergent and leveling agents :in the laundry, textile, and dyeingindustries; gas Wetting agents and detergents in the acid washing of fruit, in the acid washing of buildinggstone and brick; as a wetting agentandspreaderiin the application ofas'phalt' in road building andthe like; as a constituent of soldering flux preparations; as a notation reagent in the flotationseparation of various minerals; forzfiocculation and coagulation of various aqueous suspensions containing negatively charged particles, such assewage, coal washing waste water, and various trade wastes, and the like; as .germicides, :insecticides, emulsifiers for cosmetics, spray oils, water-repellent textile finish; etc. These-uses are by no means exhaustive, as far as industrial application goes, although the most important-use oi our new material is as a demulsifier for water-in-oil emulsions, and more specifically,emulsions of water or brine in crude petroleum.

We have found that the chemical compounds herein described, which are particularly desirable for use a demulsifiers, -may also be used as a break. inducer in doctor treatment of the kind intended to sweeten gasoline. (See U. S. Patent No. 2,157,223, dated May 9, 1939, to Sutton.)

.Cfhemical'compounds of the kind herein described are also of value as surface tension depressantsfin the acidization of calcerous oil-bearing strata by means of strong mineral acid, such as hydrochloric acid. Similarly, some members are eifective as surface tension depressants, or wetting agents, inthe flooding of exhausted oilbearing strata.

As to using compounds of the kind herein describedas flooding agents 'for recovering oil from subterranean strata, reference is made to the proceduce described-indetail in U. S. Patent No. 2,226,119, dated December 24,1940, to De Groote andKeiser. As to ,using'compounds of the kind herein'described as demulsifiers, or in particular as surface ,tension depressants, in combination with mineral acid or acidization of .oil bearing strata, reference is made to 'U. iS. Patent No. 2,233,323, dated February 25, 1941, to De-Groote and Keiser.

The new compounds herein described are of utility, not only for the purposes specifically enumerated indetail, but they'also find applica" tion in various other industries, processes, and for'various uses where wetting'agen'ts of the conventional type arensed. As to some of such additional uses which are well known, see The EX- panding Application-oi Wetting Agents, Chemical Industries, volume 48 page 324 (1941).

Another use for the compounds herein con-- templated is in the prevention of landslides, as described in U. S. Patent "No. 2,348,453, dated May 9, 194 4, to Endersby.

Reference is made to the fact that the -mate-- rials, compounds or products herein contemplated are'hydrophile in nature, and may vary from. self einulsifiahle products through the range that gives a colloidal sol, and into the final range of products which give clear solutions. Obviously, as the number of side chains in the phenolic nucleus increases, and as their length increases, the hydrophobic character both of the phenol and subsequent derivatives have been increased. If the pyridinium compound obtained from any particular experiment does not show significant hydrophile character, then such hydrophile character can be -.obtained by the verysimple qex pound, the greater thehydrophile effect. With these obvious factors in mind, there is no diflie culty in obtaining a compound having at least distinct hydrophile properties, and it may, in fact, 'asnoted, be completely water-soluble.

Attention is directed to our co-pending appli cations for patent Serial Nos. 586,262, 586,263, 586,266 and 586,267, all filed Apr.;2, 194,5 and-;allissued November 4, 194?, as Patents Nos. 2,429,996; 2,429,997; 2,430,090 and 2,430,001 ,;re-' spectively, and applications Serial Nos. 630,973 and 630,974, filed November 26,1945.

Having thus described our invention, what'we claim as new and desire to secure by Letters Patent is:

1. A hydrophile chemical compound ofEt-he formula:

Halogen in which R1 is a monocyclic phenylradical having at least 2 and not more than 3 alkylside chains, of which at least 2 contain at least A carbon atoms; the longest side chain vof the nucleus R1 shallnot contain more thanS carbon atoms, with the proviso that the number of ,carbon atoms in all the side chains must total at least '9; R20 is an alkoxy radical selected vfrom theclassconsisting of -CzI-l4O-.a nd C3HsO radicals; ,n-z's a-small whole number varying .from 1 1306; OC.R3 is the acyl radical of the low :molecular weight monocarboxy acid having not more than 3 carbon atoms, in which an alpha-hydrogen atom has been removed linked to the nitrogen of the radical NERi through its alpha carbon atom; and NERi represents a radical of a heterocyclic compound of the pyridine series selected from the group consisting of pyridine and (J-linked methyl homologs of pyridine. I

2. The compound of claim 1, wherein the halogen is chlorine.

3. The compound of'claim 1, wherein-the halogen is chlorine, and R3 is the CH2 radical.

4. The compound of claim 1, wherein the halogen is chlorine, R3 is the "CH2 radical, and n is 1.

5. The compound of gclaiml, wherein the halogen is chlorine, R3 is the CH2 radical, n is 1, and RzO-is .C2 H 40-.

.6. The compoundof claim 1, whereinthe halo.- gen is chlorine, R3 is the CH2 radical, nis "1,320 is -..C2H4O-, and NERi is a pyridinium radical.

'7. The compound of claim 1, whereinthe halo gen is chlorine, R3 is the CH2 radical, n is 1, R20 is C2H4O--, NEPA is a pyridinium radical, and at least one side chain of R1 is a butyl radical.

8. The compound of claim 1, wherein the halogen is chlorine, R3 is the CH2 radical, -n is 1,320 is --C2H4O--, NERi is a pyridinium radical and at least one side chain oi R1 is an amyl radical;

9. The compound of claim 1, wherein the halo gen is chlorine, R3 is the-CH2 radical, n is 1, R20 is -C2H4O, NERi is a pyridinium radical, and at least one side chain of R1 is an octyl radical.

MELVIN DE GRQQTE. BERNHARD KEISER.

(References on following page) Everything else- 2,517,098 9 REFERENCES CITED Number The following references are of record in the 2,233,381 file of this patent: UNITED STATES PATENTS 6 Number Name Date 1,917,258 Harris July 11, 1933 Number 2,023,075 452,866

Harris Dec. 3, 1935 10 Name Date De Groote et a1. Feb. 5, 1941 Allen et a1. Oct. 27, 1942 Blair Dec. 29, 1942 FOREIGN PATENTS Country Date Great Britain Aug. 4, 1936 

1. A HYDROPHILE CHEMICAL COMPOUND OF THE FORMULA: 